CN107974690B - Electrode and its preparation method and application and the method for preparing formic acid - Google Patents
Electrode and its preparation method and application and the method for preparing formic acid Download PDFInfo
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- CN107974690B CN107974690B CN201711192786.1A CN201711192786A CN107974690B CN 107974690 B CN107974690 B CN 107974690B CN 201711192786 A CN201711192786 A CN 201711192786A CN 107974690 B CN107974690 B CN 107974690B
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 53
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 239000002086 nanomaterial Substances 0.000 claims abstract description 40
- 230000009467 reduction Effects 0.000 claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 13
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 7
- 150000001622 bismuth compounds Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000005422 blasting Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000006722 reduction reaction Methods 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 229910000416 bismuth oxide Inorganic materials 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 229960004756 ethanol Drugs 0.000 description 10
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 229940073609 bismuth oxychloride Drugs 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- RWYPDBKDTQPOSR-UHFFFAOYSA-N OC=O.O=C=O Chemical compound OC=O.O=C=O RWYPDBKDTQPOSR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RBWFXUOHBJGAMO-UHFFFAOYSA-N sulfanylidenebismuth Chemical compound [Bi]=S RBWFXUOHBJGAMO-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to electrochemical fields, and in particular to a kind of electrode and its preparation method and application and the method for preparing formic acid.Electrode includes electrode matrix and the bismuth nano-material coating for being set to electrode matrix surface, and bismuth nano-material coating is adhered to outside electrode matrix using binder.The electrode can be effectively reduced the overpotential that carbon dioxide reduction prepares formic acid, promote reduction efficiency.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of electrode and its preparation method and application and prepare formic acid
Method.
Background technique
In recent years about electroreduction CO2More attention of the research by researcher.Electroreduction CO in aqueous solution2First processed
There are two the electrochemistry half-reaction that acid is related to is main:
Anode: H2O-2e-→2H++1/2O2 (1)
Cathode: CO2+2H++2e-→HCOOH (2)
However in cathode, evolving hydrogen reaction (2H2O+2e-→H2+2OH-Or 2H++2e-→H2) be and CO2Reduction reaction is mutual
Competition, it generates the faradic efficiency of formic acid by directly affecting, and this requires carrying out electroreduction CO2Research in maximum journey
Degree ground inhibits evolving hydrogen reaction, this is to ensure that high faradic efficiency reduction CO2The key of formic acid processed.Researchers pass through numerous studies
It was found that some higher metals of overpotential of hydrogen evolution (such as Hg, Sn, In, Pb) can reduce the influence of evolving hydrogen reaction as cathode, from
And improve the faradic efficiency for generating formic acid.However use these conventional metals as electroreduction CO2The catalyst of formic acid processed is deposited
At higher overpotential (> 1.0V), lead to low energy conversion efficiency, for example, by using Sn plate electrode, required electrolytic potential is wanted
Reach -1.8V (relative to Ag/AgCl).
Summary of the invention
The purpose of the present invention is to provide a kind of electrode, which can be effectively reduced carbon dioxide reduction and prepare formic acid
Overpotential, promoted reduction efficiency.
Another object of the present invention is to provide a kind of methods for preparing electrode, and this method preparation process is simple, and can make
The standby electrode for providing good chemical property.
Another object of the present invention is to provide a kind of electrodes to prepare the application in formic acid in catalysis reduction carbon dioxide,
It can be effectively reduced the overpotential that carbon dioxide reduction prepares formic acid, then promote the energy efficiency of reaction.
Another object of the present invention is to provide a kind of method for preparing formic acid, this method can quickly restore carbon dioxide
Formic acid, and high conversion efficiency are prepared, electrolytic potential is low.
The present invention solves its technical problem and adopts the following technical solutions to realize:
The present invention proposes that a kind of electrode, electrode include electrode matrix and the bismuth nano material painting for being set to electrode matrix surface
Layer, bismuth nano-material coating are adhered to outside electrode matrix using binder.
The present invention proposes a kind of method for preparing electrode, comprising the following steps: by bismuth nano-material coating, binder and molten
Agent is mixed into after suspension hanging drop adding to bare electrode surface.
The present invention also provides a kind of electrodes to prepare the application in formic acid in catalysis reduction carbon dioxide.
The present invention also provides a kind of methods for preparing formic acid using electrode, and the electrode catalyst reduction after activation is passed through electrolytic cell
In carbon dioxide prepare formic acid.
Electrode provided by the invention and its preparation method and application and the beneficial effect of method for preparing formic acid are: this hair
The electrode of bright offer after catalysis can quick electrolysis reduction carbon dioxide prepare formic acid, and prepare the daraf(reciprocal of farad) efficiency of formic acid
Height enables carbon dioxide to be largely reduced, meanwhile, the overpotential of preparation process is low, and the electric energy for then improving reaction turns
Change efficiency.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In the description of the present invention, it should be noted that term " first ", " second " etc. are only used for distinguishing description, without
It can be interpreted as indication or suggestion relative importance.
Electrode of the embodiment of the present invention and its preparation method and application and the method for preparing formic acid are carried out below specific
Explanation.
A kind of electrode provided in an embodiment of the present invention, electrode include that electrode matrix is received with the bismuth for being set to electrode matrix surface
Rice material coating, bismuth nano-material coating are adhered to outside electrode matrix using binder.Quickly bismuth can be received by binder
Rice material coating is adhered to formation bismuth nano-material coating on electrode matrix.
Further, bismuth nano-material coating mainly includes the bismuth compound of nano-scale, it is preferable that bismuth compound includes
Bismuth or bismuth oxide, it is further preferred that bismuth oxide includes bismuth oxide, bismuth oxychloride, bismuthyl carbonate and basic bismuth nitrate.It adopts
It can effectively ensure that the activation of subsequent electrode with above-mentioned bismuth compound, then guarantee that overpotential will not mistake when reduction carbon dioxide
Height, promoted reaction efficiency, meanwhile, above-mentioned bismuth compound be easy preparation and it is low in cost, can reduce the preparation difficulty of electrode.
Further, binder includes bonded adhesive, and the bonded adhesive is perfluorinated sulfonic resin.Perfluor sulphur
Bismuth nano-material coating can be not only adhered to electrode matrix surface by acid resin can also stablize bismuth compound, then guarantee
The reduction effect of carbon dioxide guarantees the preparation efficiency of formic acid.
The embodiment of the present invention also provides a kind of method for preparing electrode:
The processing of S1, bare electrode；
Firstly, bare electrode is processed by shot blasting, the impurity such as removal bare electrode surface dust that may be present, iron filings, after
And guarantee that bismuth nano-material coating can be acted on steadily with bare electrode, guaranteed hungry binding force between the two, prevented using electricity
Bismuth nano-material coating slides from bare electrode during pole, then guarantee carbon dioxide reduction prepare formic acid can smoothly into
Row.
The bare electrode after polishing is ultrasonically treated using solvent, the surface of bare electrode is further cleaned, so that naked electricity
Certain chemical substances for being difficult to remove that pole surface may adhere to are separated with bare electrode.Acetone and water, acetone when the solvent of use
Most organic substance can be dissolved, and also can dissolve water-soluble substances can further clean naked electricity in conjunction with ultrasound
Pole.
S2, bismuth nano-material coating is prepared；
The difference of bismuth compound used by bismuth nano-material coating is prepared, preparation process is different；
S2.1, bismuth oxide is prepared；
It is 0.1-1molL by molar concentration-1Bismuth nitrate and molar concentration be 1molL-1Ammonium hydroxide be mixed 1-
1.5 hours, and the pH value of mixed liquor is made to be 8-10, then mixed liquor reacts in the reaction kettle that temperature is 120-140 DEG C
5.5-6.5 hour.Reaction kettle cooled to room temperature after reaction, collects the sample prepared, and with distilled water and acetone
Drying at room temperature after washing 2-3 times.Three oxygen of nanometer for obtaining yellow for 1.5-2.5 hours is finally calcined in 480-520 DEG C of environment
Change two bismuths.
Bismuth nitrate and ammonium hydroxide are mixed to get basic bismuth nitrate, and then basic bismuth nitrate calcining and decomposing obtains bismuth oxide,
And extra nitrogen then produces the gases such as nitric oxide, nitrogen dioxide and is excluded, and can guarantee three oxidation of calcining using ammonium hydroxide
Impurity residual is not had during two bismuths.
S2.2, bismuth oxychloride is prepared；
Potassium chloride is added dropwise in the mixed solution of bismuth nitrate and glycerine again after bismuth nitrate is mixed with glycerine and is mixed
Stirring 10-15 minutes, using ultrasonic treatment 5-10 minutes during mixing.Then the mixed liquor of above-mentioned three is put into
It is reacted 5-6.5 hours in the reaction kettle that temperature is 105-115 DEG C.2- finally is washed to reactant respectively using distilled water and ethyl alcohol
3 times.Wherein, the molar ratio of bismuth nitrate and potassium chloride is 1:1-1.2.
S2.3, bismuthyl carbonate is prepared；
Bismuth nitrate and urea are dissolved in distilled water and dehydrated alcohol respectively, then by the above two solvent containing solute
It carries out being mixed to get mixture, and mixture is sealed, prevent urea from decomposing.Specifically using preservative film to mixing
The mixer of two kinds of solvents containing solute, such as beaker are sealed.And the time being mixed is 25-35 minutes, is mixed
Mixture is the cotton-shaped suspension of white after closing uniformly.The mixture is then heated to 85-95 DEG C in a water bath, heating time
It is 3-4 hours.After reaction, white suspension solid is obtained after reaction solution being cooled to room temperature, and is then being centrifuged 5-7 minutes,
Distilled water and ethanol washing white solid 3-4 times are recycled, impurity is removed.It is small that 10-12 is finally dried in vacuo at 55-65 DEG C
When to get nano-calcium carbonate bismuth oxide.
S2.4, basic bismuth nitrate is prepared；
It is 0.1-1molL by molar concentration-1Bismuth nitrate and molar concentration be 1molL-1Ammonium hydroxide be mixed 1-
1.5 hours, and the pH value of mixed liquor is made to be 8-10, then mixed liquor reacts in the reaction kettle that temperature is 120-140 DEG C
5.5-6.5 hour.Reaction kettle cooled to room temperature after reaction, collects the sample prepared, and with distilled water and acetone
Drying at room temperature after washing 2-3 times.
S3, electrode is prepared；
Bismuth nano-material coating, binder and solvent are mixed into suspension.Specifically, by bismuth nano-material coating with it is molten
Agent mixes dispersion after being dispersed under conditions of ultrasound with binder again.
Further, it disperses the bismuth nano-material coating being prepared in ethanol solution, and backward bismuth nanometer material
Binder is added in the mixed liquor of material coating and ethyl alcohol, and ultrasound makes bismuth nano-material coating, binder be dispersed in second
White suspension is obtained in alcohol.Wherein, the mass ratio of bismuth nano-material coating and binder is 7500-8000:1, and use is above-mentioned
Ratio can either guarantee that bismuth nano-material coating is adhered to outside bare electrode by binder, and can prevent that binder content is excessively high and leads
Causing the catalytic effect of bismuth nano-material coating reduces.
The hanging drop prepared is added into bare electrode surface and obtains required electrode.
The embodiment of the present invention also provides a kind of electrode and is preparing the application in formic acid in catalysis reduction carbon dioxide.
The embodiment of the present invention also provides a kind of method that electrode prepares formic acid；
S1, activated electrode；
The electrode that preparation is completed is activated, specifically, by electrode with -1.1V~-1.4V electricity in alkaline solution
Position reduction activation 2-30 hours.Specifically, weakly alkaline solution is that saturation has CO2Bicarbonate solution or carbonate solution,
Preferably bicarbonate solution is saleratus, the sodium bicarbonate solution that saturation has CO2, and carbonate solution is that saturation has CO2's
Solution of potassium carbonate, sodium carbonate liquor.The molar concentration of alkaline solution is 0.1-1M.Electrode can be guaranteed using above-mentioned alkalescent salt
The bismuth nano-material coating on surface is activated, meanwhile, it is activated using above-mentioned current potential, guarantees that electrode various pieces can be than filling
Divide activation, overpotential needed for reducing sequential reduction carbon dioxide.
S2, reduction carbon dioxide；
Then formic acid is prepared using the carbon dioxide that the electrode catalyst reduction after activation is passed through in electrolytic cell.
Specifically, electrolytic cell is divided into cathode can and anode slot by proton exchange membrane, is bicarbonate solution in cathode can,
Bicarbonate solution is potassium bicarbonate solution or sodium bicarbonate solution, and the molar concentration of bicarbonate solution is 0.1-1M, and electric
Pole, which is placed in cathode can, restores carbon dioxide, and carbon dioxide is constantly passed through into cathode can during electroreduction,
Reference electrode is Ag/AgCl.
And anode slot in be strong base solution, strong base solution be sodium hydroxide solution or potassium hydroxide solution, strong base solution
Molar concentration is 0.1-1M, and placement surface is coated with the electrode of titanium-based iridium ruthenium coating in anode slot.
Then CO is electrolysed at -1.2V (relative to Ag/AgCl)2, the stopping when electrolysis electricity reaches 10C, calculating CO2System
The faradic efficiency of formic acid.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of electrode provided in this embodiment, electrode include electrode matrix and the bismuth nanometer material for being set to electrode matrix surface
Expect that coating, bismuth nano-material coating are adhered to outside electrode matrix using binder.Wherein, bismuth nano-material coating is three oxidations two
Bismuth, binder are perfluorinated sulfonic resin.
The present embodiment also provides a kind of method for preparing electrode:
The processing of S1, bare electrode；
Bare electrode is processed by shot blasting, then with acetone and deionized water ultrasound.
S2, bismuth oxide is prepared；
It is 0.1molL by molar concentration-1Bismuth nitrate and molar concentration be 1molL-1Ammonium hydroxide be mixed it is 1 small
When, and the pH value of mixed liquor is made to be 8, then mixed liquor reacts 5.5 hours in the reaction kettle that temperature is 120 DEG C.Reaction knot
Reaction kettle cooled to room temperature after beam, collects the sample prepared, and with drying at room temperature after distilled water and acetone washing 2 times.
It is finally calcined 1.5 hours in 480 DEG C of environment and obtains the nanometer bismuth oxide of yellow.
S3, electrode is prepared；
It disperses the nanometer bismuth oxide coating being prepared in ethanol solution, and backward bismuth nano-material coating
Be added binder in the mixed liquor of ethyl alcohol, and ultrasound makes bismuth nano-material coating, binder evenly dispersed in ethanol
To white suspension.Wherein, the mass ratio of bismuth nano-material coating and binder is 7500:1.The suspension prepared is added dropwise
Required electrode is obtained to bare electrode surface.
The present embodiment also provides a kind of electrode and is preparing the application in formic acid in catalysis reduction carbon dioxide.
The present embodiment also provides a kind of method that electrode prepares formic acid；
S1, activated electrode；
The electrode that preparation is completed is activated, specifically, electrode is had into CO in molar concentration for 1M saturation2Potassium carbonate
It is activated 10 hours in solution with the potential reduction of -1.1V.
S2, reduction carbon dioxide；
Electrolytic cell is divided into cathode can and anode slot by proton exchange membrane, is the carbonic acid that molar concentration is 0.1M in cathode can
Hydrogen potassium solution.And electrode is placed in cathode can and restores carbon dioxide, during electroreduction constantly into cathode can
It is passed through carbon dioxide.
And in anode slot it is the solution for the potassium hydroxide that molar concentration is 0.1M, placement surface is coated with titanium-based iridium in anode slot
The electrode of ruthenium coating.
Then CO is electrolysed at -1.2V2, the stopping when electrolysis electricity reaches 10C, CO2The faradic efficiency of formic acid processed is
92%.
Embodiment 2
The structure and material of the electrode of the offer of the present embodiment and embodiment 1 be it is the same, preparation method is also essentially identical,
The difference is that the operating condition for preparing bismuth oxide of the present embodiment changes.Wherein, the molar concentration of bismuth nitrate is 1M,
The time of mixing is 1.5 hours, and the pH value of mixed liquor is 10, and the temperature of reaction is 140 DEG C, and the reaction time is 6.5 hours,
Washing times are 3 times, and the temperature of calcining is 520 DEG C, and calcination time is 2.5 hours, the matter of bismuth nano-material coating and binder
Amount is than being 8000:1.
In the method for preparing formic acid using electrode, basic operation is there is no variation, and only operating condition becomes
Change, has CO using the saturation that molar concentration is 0.2M when activated electrode2Potassium bicarbonate solution in the current potential of -1.3V also
Original activation 3 hours.It is the sodium bicarbonate solution that molar concentration is 0.1M in cathode can in reduction carbon dioxide process, in anode slot
The sodium hydroxide solution for being 0.1M for molar concentration, daraf(reciprocal of farad) efficiency is also 92%.
Embodiment 3
A kind of electrode provided in this embodiment, and basic structure and embodiment 1 are consistent, difference is the bismuth nanometer material used
Expect that coating is different, the bismuth nano-material coating that the present embodiment uses is bismuth oxychloride.
The present embodiment also provides a kind of method for preparing electrode, the preparation method basic one of the preparation method and embodiment 1
It causes, maximum difference is to prepare bismuth oxychloride.
Prepare bismuth oxychloride；
Potassium chloride is added dropwise in the mixed solution of bismuth nitrate and glycerine again after bismuth nitrate is mixed with glycerine and is mixed
Stirring 10 minutes, using ultrasonic treatment 5 minutes during mixing.The mixed liquor of above-mentioned three, which is then put into temperature, is
It is reacted 5 hours in 105 DEG C of reaction kettle.Finally reactant is washed 2 times respectively using distilled water and ethyl alcohol.Wherein, bismuth nitrate
Molar ratio with potassium chloride is 1:1.The mass ratio of bismuth nano-material coating and binder is 7800:1.
The present embodiment also provides a kind of method that electrode prepares formic acid；What this method and embodiment 1 provided prepares formic acid
Method is almost the same, the difference lies in that operating condition changes.The saturation for being 0.5M using molar concentration when polarizing electrode
There is CO2Solution of potassium carbonate in activated 12 hours with the potential reduction of -1.2V.It is to rub that cathode can is interior in reduction carbon dioxide process
Your concentration is the sodium bicarbonate solution of 0.5M, is the potassium hydroxide solution that molar concentration is 0.5M, daraf(reciprocal of farad) efficiency in anode slot
It also is 89%.
Embodiment 4
The present embodiment provides a kind of electrode, basic structure and material are consistent with the electrode that embodiment 3 provides.
The present embodiment provides a kind of method for preparing electrode, the difference of this method and embodiment 3, which is only that, prepares oxychloride
The operating condition of bismuth changes.Potassium chloride is added dropwise to the mixed of bismuth nitrate and glycerine again after bismuth nitrate is mixed with glycerine
It closes and is mixed 15 minutes in solution, using ultrasonic treatment 10 minutes during mixing.Then by the mixed of above-mentioned three
It closes liquid and is put into the reaction kettle that temperature is 115 DEG C and react 6.5 hours.Finally reactant is washed respectively using distilled water and ethyl alcohol
3 times.Wherein, the molar ratio of bismuth nitrate and potassium chloride is 1:1.2.The mass ratio of bismuth nano-material coating and binder is 7600:
1。
The present embodiment also provides a kind of method that electrode prepares formic acid；What this method and embodiment 1 provided prepares formic acid
Method is almost the same, the difference lies in that operating condition changes.The saturation for being 1M using molar concentration when activated electrode
There is CO2Sodium carbonate liquor in activated 15 hours with the potential reduction of -1.3V.It is to rub that cathode can is interior in reduction carbon dioxide process
Your concentration is the potassium bicarbonate solution of 0.8M, is the sodium hydroxide solution that molar concentration is 0.8M, daraf(reciprocal of farad) efficiency in anode slot
It also is 87%.
Embodiment 5
A kind of electrode provided in this embodiment, and basic structure and embodiment 1 are consistent, difference is the bismuth nanometer material used
Expect that coating is different, the bismuth nano-material coating that the present embodiment uses is bismuthyl carbonate.
The present embodiment also provides a kind of method for preparing electrode, the preparation method basic one of the preparation method and embodiment 1
It causes, maximum difference is to prepare bismuthyl carbonate.
Prepare bismuthyl carbonate；
Bismuth nitrate and urea are dissolved in distilled water and dehydrated alcohol respectively, then by the above two solvent containing solute
It carries out being mixed to get mixture, and mixture is sealed, prevent urea from decomposing.Specifically using preservative film to mixing
The mixer of two kinds of solvents containing solute, such as beaker are sealed.And the time being mixed is 25 minutes, mixing is equal
Mixture is the cotton-shaped suspension of white after even.The mixture is then heated to 85 DEG C in a water bath, heating time is 3 small
When.After reaction, white suspension solid is obtained after reaction solution being cooled to room temperature, and then in centrifugation 5 minutes, recycles distillation
Water and ethanol washing white solid 3 times remove impurity.10 hours are dried in vacuo at 55 DEG C finally to get nano-calcium carbonate oxidation
Bismuth.The mass ratio of bismuth nano-material coating and binder is 8000:1.
The present embodiment also provides a kind of method that electrode prepares formic acid；What this method and embodiment 1 provided prepares formic acid
Method is almost the same, the difference lies in that operating condition changes.The saturation for being 1M using molar concentration when activated electrode
There is CO2Sodium carbonate liquor in activated 30 hours with the potential reduction of -1.4V.It is to rub that cathode can is interior in reduction carbon dioxide process
Your concentration is the sodium bicarbonate solution of 1M, is the sodium hydroxide solution that molar concentration is 1M in anode slot, and daraf(reciprocal of farad) efficiency is also
86%.
Embodiment 6
A kind of electrode provided in this embodiment, and basic structure and embodiment 1 are consistent, difference is the bismuth nanometer material used
Expect that coating is different, the bismuth nano-material coating that the present embodiment uses is bismuthyl carbonate.
The preparation method of electrode provided in this embodiment is substantially consistent with the preparation method that embodiment 5 provides, and difference is
The operating condition for preparing bismuthyl carbonate is changed.The time of mixing is 35 minutes, and the temperature of heating is 95 DEG C, heating
Time is 4 hours, and centrifugation time is 7 minutes, and washing times are 4 times, and drying temperature is 65 DEG C, and drying time is 12 hours.
The present embodiment also provides a kind of method that electrode prepares formic acid；What this method and embodiment 1 provided prepares formic acid
Method is almost the same, the difference lies in that operating condition changes.It using molar concentration is the full of 1.2M when activated electrode
And have CO2Sodium bicarbonate solution in activated 2.5 hours with the potential reduction of -1.3V.Restore cathode can in carbon dioxide process
The interior potassium hydroxide solution for being the sodium bicarbonate solution that molar concentration is 0.7M, in anode slot being molar concentration is 0.7M, daraf(reciprocal of farad)
Efficiency is also 84%.
Embodiment 7
A kind of electrode provided in this embodiment, and basic structure and embodiment 1 are consistent, difference is the bismuth nanometer material used
Expect that coating is different, the bismuth nano-material coating that the present embodiment uses is basic bismuth nitrate.
The present embodiment also provides a kind of method for preparing electrode, the preparation method basic one of the preparation method and embodiment 1
It causes, maximum difference is to prepare basic bismuth nitrate.
Prepare basic bismuth nitrate；
It is 1molL by molar concentration-1Bismuth nitrate and molar concentration be 1molL-1Ammonium hydroxide be mixed it is 1.5 small
When, and the pH value of mixed liquor is made to be 10, then mixed liquor reacts 6.5 hours in the reaction kettle that temperature is -140 DEG C.Reaction
After reaction kettle cooled to room temperature, collect the sample prepared, and dry with room temperature after distilled water and acetone washing 3 times
It is dry to get nanometer-sized basic bismuth nitrate stick.The mass ratio of bismuth nano-material coating and binder is 8000:1.
The present embodiment also provides a kind of method that electrode prepares formic acid；What this method and embodiment 1 provided prepares formic acid
Method is almost the same, the difference lies in that operating condition changes.It using molar concentration is the full of 0.1M when activated electrode
And have CO2Sodium carbonate liquor in activated 6 hours with the potential reduction of -1.2V.It is in cathode can in reduction carbon dioxide process
Molar concentration is the sodium bicarbonate solution of 0.1M, is the sodium hydroxide solution that molar concentration is 0.5M in anode slot, method daraf(reciprocal of farad) the
Efficiency is 90%.
Experimental example 1
The overpotential for preparing formic acid that embodiment 1 provides is calculated, calculation formula is as follows:
η=E ° of-E (vs.Ag/AgCl) -0.20V
Wherein E ° is by CO2It is reduced to HCOO-Standard electrode potential (E °=- 0.41V vs.SHE at pH 7.0)；
Current potential of the E (vs.Ag/AgCl) when reference electrode；
Then the overpotential obtained when reduction carbon dioxide prepares formic acid is 0.59V, is gone back compared to traditional catalyst catalysis
The overpotential that former carbon dioxide prepares formic acid is higher than 1.10V, and method overpotential provided by the invention is low, improves the energy dose-effect of reaction
Rate, meanwhile, daraf(reciprocal of farad) is high-efficient.
In conclusion the electrode that 1-6 of the embodiment of the present invention is provided being capable of quick electrolysis reduction carbon dioxide after catalysis
Formic acid is prepared, and the daraf(reciprocal of farad) for preparing formic acid is high-efficient, and carbon dioxide is largely reduced, meanwhile, preparation process
Overpotential it is low, then improve the electric energy conversion efficiency of reaction.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (5)
1. a kind of method for preparing formic acid using electrode, which is characterized in that the electrode includes electrode matrix and is set to described
The bismuth nano-material coating on electrode matrix surface, the bismuth nano-material coating are adhered to the electrode matrix using binder
Outside, the bismuth nano-material coating mainly includes the basic bismuth nitrate of nano-scale,
It is 0.1-1molL that the basic bismuth nitrate, which is by molar concentration,-1Bismuth nitrate and molar concentration be 1molL-1Ammonia
Water is mixed 1-1.5 hour, and the pH value of mixed liquor is made to be 8-10, and then mixed liquor is anti-for 120-140 DEG C in temperature
Answer the bismuth compound obtained after reacting 5.5-6.5 hours in kettle；
The preparation method of the electrode includes after bismuth nano material, binder and solvent to be mixed into suspension by the suspension
It is added dropwise to bare electrode surface, by the electrode in CO2With -1.1V~-1.4V in the carbonate or bicarbonate solution of saturation
Potential reduction is used for CO after activating 2-30 hours2Electrochemical reduction formic acid.
2. the method according to claim 1 for preparing formic acid using electrode, which is characterized in that the binder includes resin
Class binder, the bonded adhesive are perfluorinated sulfonic resin.
3. the method according to claim 1 for preparing formic acid using electrode, which is characterized in that the suspension is will be described
Bismuth nano material mixes dispersion with the binder again after being dispersed under conditions of ultrasound with the solvent.
4. the method according to claim 1 for preparing formic acid using electrode, which is characterized in that the bare electrode surface is added dropwise
The bare electrode is processed by shot blasting before the suspension.
5. the method according to claim 1 for preparing formic acid using electrode, which is characterized in that the electrode catalyst after activation is also
Original is passed through the carbon dioxide in electrolytic cell and prepares formic acid, is bicarbonate solution, the electrode in the cathode can of the electrolytic cell
It is placed in the cathode can, is strong base solution in the anode slot of the electrolytic cell, placement surface is coated with titanium in the anode slot
The electrode of base iridium ruthenium coating is separated with proton exchange membrane among the cathode can and anode slot.
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